GB2032448A - Process for the manufacture of azo and hydrazo dyestuffs and certain dyes so obtained - Google Patents
Process for the manufacture of azo and hydrazo dyestuffs and certain dyes so obtained Download PDFInfo
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- GB2032448A GB2032448A GB7930572A GB7930572A GB2032448A GB 2032448 A GB2032448 A GB 2032448A GB 7930572 A GB7930572 A GB 7930572A GB 7930572 A GB7930572 A GB 7930572A GB 2032448 A GB2032448 A GB 2032448A
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- phenyl
- dyestuffs
- methyl
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- lower alkyl
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3617—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom
- C09B29/3621—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring
- C09B29/3626—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O)
- C09B29/363—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a six-membered heterocyclic with only one nitrogen as heteroatom from a pyridine ring from a pyridine ring containing one or more hydroxyl groups (or = O) from diazotized amino carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B26/00—Hydrazone dyes; Triazene dyes
- C09B26/02—Hydrazone dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The process comprises condensing an acyl hydrazine of the formula <IMAGE> with a 2,3,6-trioxotetrahydropyridine of the formula: <IMAGE> in which R is hydrogen, alkyl, aralkyl, phenyl or substituted phenyl; R<1> is methyl, phenyl or substituted phenyl; Y is carbamoyl or acetylamino; R<2> is an optionally substituted aryl group and R<3> is hydrogen, lower alkyl or aryl to produce a dyestuff of the formula: <IMAGE> The process provides a route to azo-pyridine dyestuffs which avoids the use of a two-stage diazotisation/coupling. The process also provides novel hydrazo dyestuffs in which R3 is lower alkyl or aryl and which by virtue of the presence of a lower alkyl or aryl group R<3> are fixed in the hydrazo form and are unobtainable by a diazotisation/coupling reaction. The dyestuffs are valuable for the colouration of a variety of natural and synthetic textile materials, for example polyesters, polyamides, polyacrylonitrile, cotton, wool and acetates.
Description
SPECIFICATION
Process for the manufacture of azo and hydrazo dyestuffs and certain dyes so obtained
This invention relates to a process for the manufacture of azo and hydrazo dyestuffs by the reaction of optionally N-substituted aryl hydrazines with certain 2,3,6-trioxotetrahydro pyridines and to certain hydrazo dyestuffs made by this process, which hydrazo dyestuffs are new compounds.
Thus according to the present invention there is provided a process for the manufacture of azo dyestuffs of the formula (I)
wherein R is hydrogen, alkyl, aralkyl, phenyl or substituted phenyl;
R1 is methyl, phenyl or substituted phenyl;
Y is carbamoyl or acetylamino;
R2 is an optionally substituted aryl group and
R3 is hydrogen, lower alkyl or aryl which comprises condensing an aryl hydrazine of formula
with a 2,3,6-trioxotetrahydropyridine of the formula:
The products of the present process are shown in Formula I in the hydrazo form but when R3 is hydrogen the hydrazo form will be tautomeric with the azo form and it is to be understood that in this case the invention covers the manufacture of both tautomeric forms.
Whenever the terms lower alkyl or lower alkoxy are used in this specification they mean alkyl of 1 to 4 carbon atoms and alkoxy of 1 to 4 carbon atoms respectively.
In Formula I and in the aryl hydrazine used as starting material in the process of the invention R2 may be any optionally substituted aryl group for example a phenyi or naphthyl group either of which may be substituted with any of the substituents found in the diazo components of dyestuff molecules.
Examples of such substituents which may be present in the aryl group R2 include alkyl, cycloalkyl, aralkyl, alkoxy, alkoxy, aryl carbalkoxy, acyloxy, arylazo, naphthylazo, acylamino, aryloxy, arylamino, carbamoyl, sulphamyl, alkylsuiphonyl, alkylmercapto, aralkylmercapto, dialkylamino and substituted derivatives of the foregoing and nitro, cyano, trifluoromethyl, halogeno, sulphonic acid, phosphonic acid groups and groups capable of conversion to quaternary salts.
R2 may carry one or more substituents.
R3 in Formula I above and in the aryl hydrazine used as starting material may be hydrogen, a lower alkyl group for example methyl, ethyl, n-propyl or n-butyl or an aryl group for example phenyl.
R in Formula I above and in the 2,3,6-trioxotetrahydropyridine may be hydrogen, alkyl, aralkyl, phenyl or substituted phenyl and in the cases where R is substituted phenyl the substituents on the phenyl radical are preferably lower alkyl, lower alkoxy or halogen, R may be substituted with a group capable of conversion to a quaternary salt.
Examples of R include hydrogen, methyl, ethyl, propyl, butyl, benzyl, 2-phenylethyl, phenyl, o-, mand p-tolyl, o-, m- and p-anisyl and o-, m- and p-chlorophenyl.
R1 in Formula I and in the 2,3,6-trioxotetrahydropyridine starting material may be methyl, phenyl or substituted phenyl and where R1 is substituted phenyl the substituents are preferably lower alkyl or lower alkoxy especially methyl or methoxy and are preferably in the para position.
Y in Formula I and in the 2,3,6-trioxotetrahydropyridine may be carbamoyl i.e. -CONH2 or
acetylamino i.e. -NHCOCH3.
Aryl hydrazines which may be used in the present process include:
phenyl hydrazine
o-, m- and p-nitrophenyl hydrazines o-, m- and p-chlorophenylhydrazines o-, m- and p-carboxyphenylhydrazines
o-, m- and p-sulphophenylhydrazines
phenylhydrazine-3-sulphonamide
o-chlorophenylhydrazine-4-sulphonic acid
4-methylhydrazine
4-methylhydrazine-3-sulphonic acid
2-hydroxy-3-carboxyphenylhydrazine-5-sulphonic acid
2,4-dinitrophenylhydrazine
2-hydrazinonaphthalene-6-sulphonic acid
2-hydrazinonaphthalene-4,8-disulphonic acid
4-dimethylaminophenylhydrazine dihydrochloride
3-methoxyphenylhydrazine
2,4- and 2,5-dichlorophenylhydrazine o-, m- and p-bromophenylhydrazines
a-methylphenylhydrazine -methylphenylhydrazine-4-sulphonic acid ez-butylphenylhydrazine 3-methoxy-cg-methylphenylhydrazine 4-methyl-a!-ethylphenyl hydrazine a-benzylphenylhydrazine a,,-diphenylhydrazine phenylhydrazine-3-phosphonic acid.
2,3,6-Trioxotetrahydropyridines which may be used in the process of the invention include: 5-carbamoyl-N-ethyl-4-methyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridine 5-acetylamino-N-ethyl-4-methyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridine 5-carbamoyl- 1 ,4-di methyl-2,3,6-trioxo-1 ,2,3,6-tetrahydropyridine 5-acetylamino- 1 ,4-dimethyl-2,3,6-trioxo-1 ,2,3,6-tetrahydropyridine 5-carbamoyl-N-propyl-4-methyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridi ne 5-carbamoyl-N-butyl-4-methyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridine 5-carbamoyl-4-methyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridine 5-acetylamino-N-benzyl-4-methyl-2,3,6-trioxo-1 ,2,3,6-tetrahydropyridine 5-carbamoyl-N-phenyl-4-methyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridine 5-carbamoyl-N-ethyl-4-phenyl-2,3,6-trioxo- 1 ,2,3,6-tetrahydropyridine 5-acetylamino-N-methyl-4-phenyl-2,3,6-trioxo-1 ,2,3,6-tetrahydropyridine
The condensation of the aryl hydrazine and the trioxo-tetrahydropyridine may be carried out by heating the reactants together in a solvent in the presence of a small amount of a mineral acid.
Solvents which may be used include alcohols such as formic and acetic acids and glycols such as ethylene glycol and diethylene glycol. Mixtures of solvents such as a mixture of acetic acid and ethyl alcohol may be used.
Acetic acid used alone or in admixture with another solvent is a preferred solvent for the reaction.
Preferably a small amount of a mineral acid such as hydrochloric acid or sulphuric acid is added to the reaction mixture.
The reaction is conveniently carried out at the boiling point of the solvent or at a temperature of 800 to 1 500C.
The product may be isolated by conventional methods.
The process of the present invention provides a route to the preparation of azo-pyridine dyestuffs which avoids the use of the two stage diazotisation/coupling route. In the case of those products of the process wherein R3 is lower alkyl or aryl, the process provides novel hydrazo dyestuffs which by virtue of the presence of the lower alkyl or aryl group R3 are fixed in the hydrazo form and are unobtainable by the diazotisation/coupling reaction.
Thus according to a further feature of the present invention there are provided novel dyestuffs of the formula
wherein R, R', R2 and Y are as hereinbefore defined and R4 is lower alkyl or aryl.
The dyestuffs made by the process of the invention are valuable for the colouration of a variety of natural and synthetic textile materials, for example polyesters, polyamides, polyacrylonitrile, cotton, wool and acetates.
The invention is illustrated by the following Examples in which all parts are by weight except where otherwise stated.
EXAMPLE 1
A mixture of 2.0 parts of 5-carbamoyl-N-ethyl-4-methyl-2,3,6-trioxo-1 ,2,3,6-tetrahydropyridine and 1.02 parts of 2,4-dinitrophenylhydrazine in 50 parts of ethyl alcohol and 3 drops of conc.
hydrochloric acid (360Tw) are boiled under a reflux condenser for 30 minutes. The precipitated solid is filtered off, washed with methyl alcohol and dried to yield 2.0 g of 3-carbamoyl-5-[2,4dinitrophenylazo]-N-ethyl-4-methyl-6-hydroxypyrid-2-one. On analysis the product was found to contain C = 46.5%; H = 3.5%; N = 21.4%. C1sH14N6o7 requires C = 46.2%; H = 3.6%; N = 21.5%.
EXAMPLE 2
If in place of the 2,4-dinitrophenylhydrazine used in Example 1 there are used 1.53 parts of onitrophenylhydrazine there is obtained 1.5 parts of 3-carbamoyl-5-[o-nitrophenylazo]-N-ethyl-4- methyl-6-hydroxypyrid-2-one. This product was shown to be identical to the product obtained by coupling diazotised o-nitroaniline with 3-carbamoyl-N-ethyl-4-methyl-6-hydroxypyrid-2-one by comparison of their infra red spectra and examination by thin layer chromatography.
EXAMPLES 3-13 Examples 3-13 of the invention are detailed in the following Table when the hydrazine in column II is condensed with the trioxo compound in column Ill by the method described in Example 1 to give the hydrazone or azo compound listed in column IV.
II III IV Example Hydrazine Trioxo Compound Azo/Hydrazine 3 α-methylphenylhydrazine- 5-carbamoyl-N-ethyl-4- 5-carbamoyl-2,6-dioxo-14-sulphonic acid methyl-2,3,6-trioxo- ethyl-4-methyl-3-[N'methyl1,2,3,6-tetrahydro- N'-(3-sulphophenyl)hydrazo]pyridine 1,2,3,6-tetrahydropyridine 4 m-chlorophenyl 5-acetylamino-N-ethyl- 5-acetylamino-3-(3-chlorohydrazine 4-methyl-2,3,6-trioxo- phenylazo)-1-ethyl-61,2,3,6-tetrahydro- hydroxy-4-methylpyrid -2pyridine one 5 4-sulphophenylhydrazine 5-carbamoyl-1,4-dimethyl- 5-carbamoyl-1,4-dimethyl2,3,6-trioxo-1,2,3,6- 6-hydroxy-4-methyl-3-(4tetrahydropyridine sulphophenylazo)-pyrid-2one 6 phenylhydrazine-3- 5-acetylamino-1,4- 5-acetylamino-1,4-dimethylsulphonamide dimethyl-2,3,6-trioxo- 6-hydroxy-4-methyl-3-(31,2,3,6-tetrahydro- sulphonamidophenylazo)pyridine pyrid-2-one 7 4-methylphenylhydrazine- 5-carbamoyl-N-propyl- 5-carbamoyl-6-hydroxy-43-sulphonic acid 4-methyl-2,3,6-trioxo- methyl-3-(4-methylphenyl1,2,3,6-tetrahydro- azo)-1-n-propylpyrid-2pyridine one
II III IV Example Hydrazine Trioxo Compound Azo/Hydrazine 8 a-methylphenylhydrazine 5-carbamoyl-N-butyl-4- 1-n-butyl-5-carbamoyl-2,6methyl-2,3,6-trioxo- dioxo-4-methyl-3-(N'-methyl1,2,3,6-tetrahydro- N'-phenylhydrazo)-1,2,3,6pyridine tetrahydropyridine 9 phenylhydrazine-3- 5-carbamoyl-4-methyl- 5-carbamoyl-4-methyl-3phosphonic acid 2,3,6-trioxo- (phenylazo-3-phosphonic 1,2,3,6-tetrahydro- acid)-2,6-dihydroxypyridine pyridine 10 a,a-diphenylhydrazine 5-acetylamino-N-benzyl- 5-acetylamino-1-benzyl-2,64-methyl-2,3,6-trioxo- dioxo-3-(N,N'-diphenyl1,2,3,6-tetrahydro- hydrazo)-4-methyl-1,2,3,6pyridine tetrahydropyridine 11 3-methoxyphenylhydrazine 5-carbamoyl-N-phenyl- 5-carbamoyl-4-methyl-3-(34-methyl-2,3,6-trioxo- methoxyphenylazo)-1-phenyl1,2,3,6-tetrahydro- 6-hydroxypyrid-2-one pyridine 12 a-benzylphenylhydrazine 5-carbamoyl-N-ethyl-4- 3-(N-benzyl-N-phenylphenyl-2,3,6-trioxo- hydrazo)-5-carbamoyl-11,2,3,6-tetrahydro- ethyl-4-phenyl-2,6-dioxopyridine 1,2,3,6-tetrahydropyridine 13 2-hydrazinonaphthalene- 5-acetylamino-N-methyl 4- 5-acetylamino-1-methyl-36-sulphonic acid phenyl-2,3,6-trioxo- (6-sulphonaphth-2-ylazo)1,2,3,6-tetrahydro- 4-phenyl-6-hydroxypyridpyridine 2-one
Claims (8)
1. A process for the manufacture of azo dyestuffs of the formula (I)
wherein R is hydrogen, alkyl, aralkyl, phenyl or substituted phenyl;
R1 is methyl, phenyl or substituted phenyl;
Y is carbamoyl or acetylamino;
R2 is an optionally substituted aryl group and
R3 is hydrogen, lower alkyl or aryl which comprises condensing an aryl hydrazine of formula
with a 2,3,6-trioxotetrahydropyridine of the formula:
2. A process as claimed in claim 1 in which the substituent on the phenyl radical, when R is substituted phenyl, is lower alkyl, lower alkoxy or halogen.
3. A process as claimed in claim 1 or claim 2 in which the substituent on the phenyl radical, when
R1 is substituted phenyl, is lower alkyl or lower alkoxy.
4. A process as claimed in any one of the preceding claims in which the acyl hydrazine is condensed with the trioxo-tetrahydropyridine in a solvent in the presence of a small amount of mineral acid.
5. A process as claimed in claim 4 in which the solvent is acetic acid either used alone or in admixture with another solvent.
6. A process as claimed in claim 1 substantially as described in any one of Examples 1 to 13.
7. Dyestuffs of the formula:
wherein R, R1, R2 and Y have the meanings given in claim 1 and R4 is lower alkyl or aryl.
8. Dyestuffs as claimed in claim 7 whenever prepared by the process claimed in any one of claims 1 to 6.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3668378 | 1977-09-02 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2032448A true GB2032448A (en) | 1980-05-08 |
| GB2032448B GB2032448B (en) | 1982-11-03 |
Family
ID=10390325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7930572A Expired GB2032448B (en) | 1977-09-02 | 1979-09-04 | Process for the manufacture of azo and hydrazo dyestuffs and certain dyes so obtained |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2032448B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8211606B2 (en) | 2007-03-19 | 2012-07-03 | Canon Kabushiki Kaisha | Coloring compound, yellow toner, sheet for heat-sensitive transfer recording, and ink |
-
1979
- 1979-09-04 GB GB7930572A patent/GB2032448B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8211606B2 (en) | 2007-03-19 | 2012-07-03 | Canon Kabushiki Kaisha | Coloring compound, yellow toner, sheet for heat-sensitive transfer recording, and ink |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2032448B (en) | 1982-11-03 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |